CN1252171C - Elastomer compsns. for olefines elastomer crosslinked foaming body - Google Patents

Elastomer compsns. for olefines elastomer crosslinked foaming body Download PDF

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Publication number
CN1252171C
CN1252171C CNB021064679A CN02106467A CN1252171C CN 1252171 C CN1252171 C CN 1252171C CN B021064679 A CNB021064679 A CN B021064679A CN 02106467 A CN02106467 A CN 02106467A CN 1252171 C CN1252171 C CN 1252171C
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Prior art keywords
ethylene
record
mfr
crosslinked foam
astm
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CN1369520A (en
Inventor
末田公宣
八坂直登
柳徖善
尹晸植
崔景满
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Mitsui Chemicals Inc
Mitsui Chemical Industry Co Ltd
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Mitsui Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • A—HUMAN NECESSITIES
    • A43—FOOTWEAR
    • A43B—CHARACTERISTIC FEATURES OF FOOTWEAR; PARTS OF FOOTWEAR
    • A43B17/00—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined
    • A43B17/14—Insoles for insertion, e.g. footbeds or inlays, for attachment to the shoe after the upper has been joined made of sponge, rubber, or plastic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene

Abstract

The elastomeric composition for preparing an olefinic elastomer crosslinked foam according to the present invention contains an ethylene/alpha-olefin copolymer (A) having a specific density and MFR, an organic peroxide (D), a crosslinking assistant (E), a foaming agent (F), an organic metal compound (G), and as necessary, a high pressure low density polyethylene (B) having a specific MFR, and an ethylene/vinyl acetate copolymer (C) having a specific amount of vinyl acetate and a specific MFR. An olefinic elastomer crosslinked foam of the present invention can be obtained by crosslinking and foaming the above composition. Further, another olefinic elastomer crosslinked foam of the present invention can be obtained by a secondary compression of the above crosslinked foam. The footwear part of the present invention is made of these crosslinked foams. The present invention provides an elastomeric composition for preparing an olefinic elastomer crosslinked foam that can provide an olefinic elastomer crosslinked foam having an Asker C hardness of 20 to 80, a low specific gravity, a low compression set (CS), and excellent tear strength and impact resilience; and a crosslinked foam made of this. Furthermore, the present invention provides footwear parts made of the above crosslinked foam.

Description

Olefin type elastomer crosslinked foaming body and function elastic composition and uses thereof
Technical field that the present invention belongs to
The present invention relates to olefin type elastomer crosslinked foaming body and function elastic composition and uses thereof, in more detail, relate to and to provide ア ス カ one C hardness in 20～80 scopes, and low-gravity, (CS) is little in compression set, and the olefin type elastomer crosslinked foaming body and function elastic composition of the outstanding olefin type elastomer crosslinked foam of tear strength characteristic and resilience elasticity, and olefin type elastomer crosslinked foam.
Background technology
In order to obtain low-gravity is light weight and softish, the resin that physical strength is high, and the technology of using crosslinked foam is widely used in trolley part, wrapping material, the daily necessities etc. such as interior material or door glass tie point at building interior and exterior finishes material.In order to realize lightweight, only resin expanded meeting is caused physical strength to reduce, by the crosslinking reaction of resin, make the molecular chain combination, like this, can suppress the reduction of physical strength, and realize lightweight by foaming.
In addition, in the sole (mainly being the middle level sole) of sports shoes etc., also use the crosslinked foam of resin, this is because need light weight, suppress the distortion that life-time service causes, and the material with physical strength of standing abominable working conditions.
In the past, in sole, though the crosslinked foam of known use ethene vinyl-acetic ester multipolymer, but the crosslinked foam that uses this ethene vinyl-acetic ester copolymer compositions to be shaped, because the proportion height, and low compression set is poor, during for example as sole, exist to weigh, and because life-time service causes that sole is compressed, the problem of physical strengths such as forfeiture resilience elasticity.
Te Biaoping 9-501447 communique, spy open flat 11-206406 communique and have put down in writing respectively and relate to the crosslinked foam that uses ethylene, the invention of the crosslinked foam of the mixture of use ethene vinyl-acetic ester multipolymer and ethylene, but in these inventions, though low-gravity and low permanent compression set are improved, fail to obtain satisfied performance.
Therefore, wish to find to provide ア ス カ one C hardness in 20～80 scopes, and low-gravity, (CS) is little in compression set, and the olefin type elastomer crosslinked foaming body and function elastic composition of the outstanding olefin type elastomer crosslinked foam of tearing toughness characteristic and resilience elasticity, and crosslinked foam.
Goal of the invention
The present invention is in order to solve the invention of above-mentioned problems of the prior art, its objective is to provide to provide ア ス カ one C hardness in 20～80 scopes, and low-gravity, (CS) is little in compression set, and the olefin type elastomer crosslinked foaming body and function elastic composition of the outstanding olefin type elastomer crosslinked foam of tearing toughness characteristic and resilience elasticity, and crosslinked foam.
In addition, the purpose of this invention is to provide the footwear parts that form by above-mentioned olefin type elastomer crosslinked foam, sole for example, the middle level sole of footwear, the internal layer sole of footwear, sandals.
Summary of the invention
The hydrocarbon elastomer crosslinked foaming body and function elastic composition that the present invention relates to is characterized in that, contains
Density (ASTM D 1505) is 880～920kg/m 3, melt flow (1238,190 ℃ of ASTM D, 2.16kg loading) MFR 216Be 0.1～10g/10 minute ethylene (A),
Organo-peroxide (D),
Crosslinking coagent (E),
Whipping agent (F) and
Organometallic compound (G),
This organometallic compound (G) is the metallic compound that is selected from the periodic table of elements 2～12 families, has 2 groups that have the unsaturated link(age) between the carbon atom and be selected from least a atom of O, S and N in a part at least.
Said composition, with respect to aforementioned ethylene (A) 100 weight parts, also can further contain melt flow (ASTM D 1238,190 ℃, 2.16kg loading) be 0.1～50g/10 minute high-pressure process new LDPE (film grade) (B) 5～100 weight parts, and/or vinyl-acetic ester content is 10～30 weight %, melt flow (ASTM D 1238,190 ℃, 2.16kg loading) is 0.1～50g/10 minute ethene vinyl-acetic ester multipolymer (C) 5～1900 weight parts.
Alpha-olefin in the aforementioned ethylene (A), the normally alpha-olefin of carbonatoms 3～10.
As aforementioned ethylene (A), can use the molecular weight distribution of obtaining by gel permeation chromatography (GPC) more than 2 kinds (Mw/Mn) in 1.5～4 scopes, and melt flow (1238,190 ℃ of ASTM D, 2.16kg loading) MFR 2.16And melt flow (1238,190 ℃ of ASTM D, 10kg loading) MFR 10Ratio (MFR 10/ MFR 216) the mixture of ethylene in 5～20 scopes.
Aforementioned more than 2 kinds the mixture of ethylene preferred, the molecular weight distribution of obtaining by GPC (Mw/Mn) is in 2.3～6 scopes, by mixing or the multi-stage polymeric manufacturing.
Aforementioned organometallic compound (G) has 2 CH usually at least in a part 2=CH-CO-O-base or CH 2=C (CH 3)-CO-O-base.
As aforementioned organometallic compound (G), preferred organic zinc compound.
As aforementioned organic zinc compound preferably dizinc acrylate resin and zinc dimethacrylate.
In aforementioned elastic composition, measure 100 weight parts with respect to the total of ethylene (A), high-pressure process new LDPE (film grade) (B) and ethene vinyl-acetic ester multipolymer (C), contain aforementioned organometallic compound (G) 0.05～5 weight part.But condition is, component (B) and component (C) are any components, and their combined amount can be 0 weight part.
The olefin type elastomer crosslinked foam that the present invention relates to is characterized in that, is the aforementioned alkene body class elastomer crosslinked foaming body that the present invention relates to is obtained with the elastic composition crosslinked foaming.
In addition, the olefin type elastomer crosslinked foam that the present invention relates to can be that the aforementioned crosslinked foam that the present invention relates to is carried out the crosslinked foam that second-compressed obtains.
Aforementioned second-compressed is normally at 130 ℃～200 ℃ of temperature, 30～300kgf/cm 2Loading is carried out under 5～60 minutes the condition.
These crosslinked foams, preferred specific gravity (JIS K 7222 (g/cm 3)) be 0.05～0.25, surface hardness (ア ス カ one C hardness) is 20～80, the gel ratio is more than 70%.
The footwear parts that the present invention relates to is characterized in that, are made by the aforementioned olefin type elastomer crosslinked foam that the present invention relates to.
As aforementioned footwear parts, can enumerate for example middle level sole, internal layer sole, sole etc.
Detailed Description Of The Invention
Below, the olefin type elastomer crosslinked foaming body and function composition and use thereof that the present invention relates to is specifically described.
The olefin type elastomer crosslinked foaming body and function elastic composition that the present invention relates to is, carry out the uncrosslinked not foaming composition of crosslinked foaming by heating, by specific ethylene (A), organo-peroxide (D), crosslinking coagent (E), whipping agent (F), organometallic compound (G) and high-pressure process new LDPE (film grade) (B) as required, ethene vinyl-acetic ester multipolymer (C) forms.
Ethylene (A)
The ethylene (A) that uses in the present invention is the low-crystalline random copolymers of the alpha-olefin formation of ethene and carbonatoms 3～10, and density (ASTM D 1505) is 880～920kg/m 3, melt flow (1238,190 ℃ of ASTM D, 2.16kg loading) MFR 216Be 0.1～10g/10 minute, preferred 0.5～10g/10 minute, more preferably 0.5～5g/10 minute.
In addition, the molecular weight distribution (Mw/Mn) obtained by gel permeation chromatography (GPC) of optimal ethylene alpha-olefin copolymer (A) is in 1.5～4 scopes.If use the ethylene (A) of molecular weight distribution (Mw/Mn) in above-mentioned scope, can obtain to prepare the composition of the outstanding elastomer crosslinked foaming body of low compression set and mechanical strength property.
Above-mentioned molecular weight distribution (Mw/Mn) is used the following mensuration of GPC-150C of ミ リ Port ア society system.
Separator column is TSK GNH HT, column dimension is that diameter is 72mm, long 600mm, column temperature is 140 ℃, mobile phase is used orthodichlorobenzene (with the pure pharmaceutical worker's industry of light (strain) system) and is made BHT (military field pharmaceutical industries (strain) system) the 0.025 weight % of antioxidant, moves sample with 1.0ml/ minute speed, and sample solution concentration is 0.1 weight %, the sample injection rate is 500 microlitres, and detector uses differential refractometer.Mw, Mn use existing EPR as standard model, determining molecular weight.
With the alpha-olefin of ethylene copolymer be the alpha-olefin of carbonatoms 3～10, specifically can enumerate propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc.Wherein preferred propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene.These alpha-olefins can use separately, also can be used in combination more than 2 kinds.
Ethylene (A) contains from the unit that ethene imports and is generally 85～99 moles of %, the amount of preferred 85～98 moles of %, and containing from carbonatoms is that the unit that the alpha-olefin of 3-10 imports is generally 1～15 mole of %, the amount of preferred 2～15 moles of %.
The composition of ethylene alpha-olefin interpolymers (A) is usually by measuring 120 ℃ of temperature, measure frequency 25.05MHz, spectrum width 1500Hz, pulse cycle time 4.2sec., be determined in the sample tube of 10mm φ under the condition of pulse width 6 μ sec, the ethylene of 200mg is solved homogeneously in sample in the 1ml hexachlorobutadiene 13The decision of C-NMR spectrum.
In addition, ethylene (A) except these unit, in the scope of not damaging the object of the invention, also can contain the unit that imports from other polymerizable monomer.
Use ethylene, propylene random copolymers, ethene 1-butylene random copolymers as ethylene alpha-olefin interpolymers (A) is preferred, ethylene, propylene 1-butylene random copolymers, ethene 1-hexene random copolymers, ethene 4-methyl-1-pentene random copolymers, ethene 1-octene random copolymers etc.These multipolymers can more than 2 kinds and be used.
In the present invention, the preferred melt flow of flow characteristics of ethylene (A) (1238,190 ℃ of ASTM D, 2.16kg loading) MFR 216And melt flow (1238,190 ℃ of ASTM D, 10kg loading) MFR 10Ratio (MFR 10/ MFR 216) in 5～20 scopes.
In addition, as ethylene (A), use composition also capable of being combined, the different ethylene more than 2 kinds of molecular weight.For example, preferred density (ASTM D 1505) is 880～900kg/m 3Melt flow (1238,190 ℃ of ASTM D, 2.16kg loading) is 0.1～50g/10 minute, ethylene (A-1) 5～95 weight parts of molecular weight distribution (Mw/Mn) in 1.5～4 scopes of obtaining by GPC and, density (ASTM D 1505) is 900～920kg/m 3Melt flow (ASTM D 1238,190 ℃, 2.16kg loading) be 0.1～50g/10 minute, the composition that ethylene (A-2) 5～95 weight parts [the total amount of two kind multipolymers be 100 weight parts] of molecular weight distribution (Mw/Mn) in 1.5～4 scopes of obtaining by GPC form.These multipolymers (A-1), (A-2) can use more than 2 kinds respectively.
The composition that above-mentioned ethylene more than 2 kinds forms, preferably the molecular weight distribution of obtaining by GPC (Mw/Mn) is in 2.3～6 scopes.
Above-mentioned ethylene (A) can be by using the known method preparation of palladium class catalyzer, titanium class catalyzer or aromatic ring alkene metal derivative class catalyzer etc.
In addition,, can select, or pass through any method of the method for multi-stage polymeric polymerization different compositions these component blended methods for obtaining the composition that said components (A-1) and component (A-2) form.
High-pressure process new LDPE (film grade) (B)
In the present invention, the high-pressure process new LDPE (film grade) (B) of Shi Yonging is known tubular reactor machine before adopting, reaction under high pressure machine as required, with the alpha-olefin of ethene or ethene and carbonatoms 3～10 in the presence of the random polymerization catalyzer, the polyvinyl resin made of random polymerization under high pressure.
With the alpha-olefin of ethylene copolymer, be the alpha-olefin of carbonatoms 3～10, specifically can enumerate propylene, 1-butylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene etc.Wherein preferred propylene, 1-butylene, 1-hexene, 4-methyl-1-pentene, 1-octene.These alpha-olefins can use separately, also can be used in combination more than 2 kinds.
High-pressure process new LDPE (film grade) (B) can contain the unit that the alpha-olefin from carbonatoms 3～10 of 1 mole of % of less than amount imports.
The composition of high-pressure process new LDPE (film grade) (B) can use the method decision identical with the composition measuring method of aforementioned ethylene (A).
High-pressure process new LDPE (film grade) (B), density (ASTM D 1505) is generally 910～930kg/m 3, preferred 915～930kg/m 3, more preferably 915～925kg/m 3
Melt flow (the MFR of high-pressure process new LDPE (film grade) (B); ASTM D 1238, the 2.16kg loading, 190 ℃) at 0.1～50g/10 minute, preferred 0.5～20g/10 minute, more preferably in 0.5～10g/10 minute the scope.If this melt flow in above-mentioned scope, can obtain to provide the outstanding composition of plasticity of high-intensity crosslinked foam.
High-pressure process new LDPE (film grade) (B), with respect to ethylene (A) 100 weight parts, as required, and can be with 5～100 weight parts, preferred 10～70 weight parts, more preferably the ratio of 15～45 weight parts is used.If use high-pressure process new LDPE (film grade) (B), can obtain to be provided at the elastic composition of the outstanding crosslinked foam of high strength tear strength characteristic according to aforementioned proportion.
Ethene vinyl-acetic ester multipolymer (C)
In the present invention, the ethene vinyl-acetic ester multipolymer (C) of Shi Yonging is that ethene and vinyl-acetic ester copolymerization obtain as required.
The vinyl-acetic ester amount of ethene vinyl-acetic ester multipolymer (C) is 10～30 weight %, preferred 15～30 weight %, more preferably 15～25 weight %.
In addition, the melt flow (MFR of this ethene vinyl-acetic ester multipolymer (C); ASTM D1238,, 190 ℃ of 2.16kg loadings) be 0.1～50g/10 minute, preferred 0.5～20g/10 minute, more preferably 0.5～10g/10 minute.
Ethene vinyl-acetic ester multipolymer (C), with respect to ethylene (A) 100 weight parts, as required, and can be with 0～1900 weight part, the ratio of preferred 5～1900 weight parts is used.If use ethene vinyl-acetic ester multipolymer (C), can obtain to provide the elastic composition of the outstanding crosslinked foam of tear strength characteristic according to aforementioned proportion.
Organo-peroxide (D)
As the organo-peroxide (D) that uses as linking agent in the present invention, specifically can enumerate dicumyl peroxide; ditertiary butyl peroxide, 2,5-dimethyl-2; 5-two (t-butyl peroxy) hexane, 2,5-dimethyl-2; 5-two (t-butyl peroxy) hexin-3, two (t-butyl peroxy sec.-propyl) benzene of 13-, 1; two (t-butyl peroxy)-3,3 of 1-, the 5-trimethyl-cyclohexane; normal-butyl-4; two (t-butyl peroxy) valerates of 4-, benzoyl peroxide, p-chlorobenzoyl peroxide; 2; the 4-dichlorobenzoperoxide, BPIC (t butyl peroxy isopropyl carbonate), diacetyl peroxide; lauryl peroxide, tertiary butyl cumenyl superoxide etc.
In the present invention, organo-peroxide (D), total with respect to ethylene (A), high-pressure process new LDPE (film grade) (B) and ethene vinyl-acetic ester multipolymer (C) is measured 100 weight parts, and usually with 0.1～1.5 weight part, the ratio of preferred 0.2～1.0 weight part is used.If together, use the crosslinked foam that can obtain having appropriately crosslinked structure according to aforementioned proportion with organo-peroxide (D) and crosslinking coagent (E).
Crosslinking coagent (E)
As the crosslinking coagent that uses in the present invention (E), specifically can enumerate, Sulfur, p-benzoqui(o)none dioxime, p, p '-dibenzoyl benzoquinones dioxime, N-methyl-N-dinitrosoaniline, nitrosobenzene, diphenylguanidine, TriMethylolPropane(TMP)-N, a N '-benzene two maleic anhydrides peroxide crosslinking coagents such as imines that contract; Or Vinylstyrene, triallyl cyanurate (TAC), triallyl isocyanate (TAIC).In addition, can enumerate ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, multifunctional methacrylate monomer such as allyl methyl acrylate, polyfunctional vinyl monomers such as vinyl butyrate, vinyl stearate ester etc.Wherein, preferred triallyl cyanurate (TAC), triallyl isocyanate (TAIC).
In the present invention, above-mentioned crosslinking coagent (E), preferably the weight ratio [(E)/(D)] with crosslinking coagent (E) and organo-peroxide (D) is 1/30～5/1, and is preferred 1/20～3/1, more preferably 1/15～2/1 amount is used.
Whipping agent (F)
As the whipping agent (F) that uses in the present invention, specifically can enumerate azoformamide (ADCA), N, N '-dinitrosopentamethylene tetramine, 4,4 '-oxygen two (benzol sulfohydrazide), sulfobenzide-3,3 '-disulfonyl hydrazide, p-toluene sulfonylsemicarbazide, organic thermolysis type whipping agents such as three hydrazides, three bifurcation piperazines, sodium bicarbonate, yellow soda ash, bicarbonate of ammonia, inorganic thermolysis type such as volatile salt whipping agent.Wherein, preferred especially nitrogen benzide formyl (ADCA), sodium bicarbonate.
In the present invention, whipping agent (F) is measured 100 weight parts with respect to the total of ethylene (A), high-pressure process new LDPE (film grade) (B) and ethene vinyl-acetic ester multipolymer (C), usually with 3～20 weight parts, the ratio of preferred 5～15 weight parts is used.If use whipping agent (F) according to aforementioned proportion, can obtain expansion ratio and the high foam molding of separated foam degree.The usage quantity of whipping agent (F) will be considered the expansion ratio decision of crosslinked foam.
Organometallic compound (G)
The organometallic compound of Shi Yonging (G) in the present invention has 2 groups with atom of unsaturated link(age) and at least a O of being selected from, S and N between the carbon atom at least in a molecule.
The metal of this organometallic compound (G) is the metal that is selected from the periodic table of elements 2～12 families.Wherein, the metal of 3～12 families belongs to transition metal.That is, the metallic compound of 3～12 families is organo-transition metal compounds.In the present invention, preferred 2 genus, 12 metals that belong to, wherein, preferred Mg, Zn, preferred especially Zn.
As group, preferably has the group of the structure that O, S or N atom directly be connected with atoms metal, more preferably unsaturated aliphatic carboxyl, especially preferably CH with atom of unsaturated link(age) and at least a O of being selected from, S and N between the carbon atom 2=CH-CO-O-, CH 2=C (CH 3)-CO-O-.
As the organometallic compound (G) that uses in the present invention, as in a molecule, having 2 CH at least 2=CH-CO-O-base or CH 2=C (CH 3The organometallic compound of)-CO-O-base, preferred organic zinc compound.Dizinc acrylate resin (ZDA) shown in the concrete preferred following formula, or the zinc dimethacrylate shown in the following formula (ZDMA).
(CH 2＝CH-CO-O-) 2Zn
(CH 2＝C(CH 3)-CO-O-) 2Zn
In addition, ZDA abbreviates " zinc acrylate resin " sometimes as.Equally, ZDMA also abbreviates " zinc methacrylate " sometimes as.
Organometallic compound (G) for example comprises also that metal oxide such as zinc oxide and, organic compound such as vinylformic acid, methacrylic acid are reflected at the situation of the inner formation of composition with the component of aforementioned (A)～(F) by melt compounding.
Above-mentioned organometallic compound (G), total with respect to ethylene (A), high-pressure process new LDPE (film grade) (B) and ethene vinyl-acetic ester multipolymer (C) is measured 100 weight parts, usually with 0.05～5 weight part, preferred 0.05～4 weight part, more preferably the ratio of 0.1～2 weight part is used.If use organometallic compound (G) according to aforementioned proportion, since the gel ratio height of gained crosslinked foam, the trickle homogeneous of mesh that therefore foams, and its result has improved the compression tension set, tear strength characteristic, mechanical-physical character such as resilience elasticity.
The olefin type elastomer crosslinked foam
The olefin type elastomer crosslinked foam that the present invention relates to, as mentioned above, can be by the olefin type elastomer crosslinked foaming body and function elastic composition crosslinked foaming that will the present invention relates to, usually at 130～200 ℃, 30～300kgf/cm 2, crosslinked foaming obtains under 10～90 minutes the condition.Just, because the time-dependent of crosslinked foaming in the thickness of mould, therefore can surpass this scope, suitably increase and decrease obtains.
In addition, the olefin type elastomer crosslinked foam that the present invention relates to, also can be molding with crosslinked foaming under these conditions at 130～200 ℃, 30～300kgf/cm 2, 5～60 minutes, compression ratio 1.1～3, the crosslinked foam that preferred 1.3～2 condition lower compression is shaped and obtains.
These crosslinked foams, proportion (JIS K 7222) is 0.05～0.25, surface hardness (ア ス カ one C hardness; JIS S 6050) in 20～80 scope, the gel ratio is more than 70%, to be generally more than 80～99%.
The olefin type elastomer crosslinked foam that the present invention relates to such rerum natura, it is little to have compression set, tear strength height, the characteristic that resilience elasticity is high.
In addition, above-mentioned gel ratio (gel content; Dimethylbenzene is dissolved constituent not), following mensuration.
Weighing olefin type elastomer crosslinked foam sample chops up, and then the gained shred is put into encloses container with dimethylbenzene, refluxes 3 hours.
Then, the sample taking-up is placed on the filter paper, makes it adiabatic drying.(value of) weight for example, weighting material, weighting agent, pigment etc. is as " final weight of revisal (Y) " to deduct dimethylbenzene indissolvable component beyond the polymeric constituent from the weight of this drying residue.
On the other hand, (for example deduct the weight of xylene soluble component beyond the polymeric constituent (for example, stablizer etc.) and the dimethylbenzene indissolvable component beyond the component of polymer from the weight of sample, weighting material, weighting agent, pigment etc.) value of weight is as " the initial stage weight (X) of revisal ".
Here, gel content (dimethylbenzene indissolvable component) is obtained by following formula.
Gel content [weight %]=[final weight of revisal (Y)] ÷ [the initial stage weight (X) of revisal] * 100
The preparation of olefin type elastomer crosslinked foam
Olefin type elastomer crosslinked foam of the present invention for example can prepare with the following method.
The each component of the olefin type elastomer crosslinked foaming body and function elastic composition that the invention described above is related to mixes in half shell milling device, carries out melt compounding in Banbury mixer, roller, forcing machine.When hot melt is mixing, must below the decomposition temperature of whipping agent (F), organo-peroxide (D) (linking agent), mix, specifically, the temperature that reaches composition hot melt state that must impose a condition is 100～140 ℃, with the mixing homogeneous that reaches of composition.
In the said composition, except above-mentioned ethylene (A), high-pressure process new LDPE (film grade) (B), ethene vinyl-acetic ester multipolymer (C), organo-peroxide (D), crosslinking coagent (E), whipping agent (F) and organometallic compound (G) in addition can be in the scopes of not damaging the object of the invention, mix weighting materials such as talcum, lime carbonate, aluminium hydroxide, magnesium hydroxide as required, heat-resisting stabilizing agent, weather-proof stablizer, fire retardant, the hydrochloric acid sorbent material, pigment, the sliding material that flows, various additives such as antiseize paste.
The sheet material of the olefin type elastomer crosslinked foaming body and function elastic composition that the present invention relates to for example can be with the mixture that obtains by above-mentioned blending means calendaring molding machine, Press forming machine, and T type forcing machine makes.When this sheet material is shaped, be necessary the following shaping sheet material of decomposition temperature at whipping agent (F), organo-peroxide (D), specifically, the temperature of the hot melt state that reaches composition of being necessary to impose a condition is 100～140 ℃, the shaping sheet material.
Will be with the composition of aforesaid method sheet materialization, severing is with respect to 1.0～1.2 times of range size of mold volumes, inserts in the mould that remains on 130～200 ℃.Mold pressure at mould is 30～300kgf/cm 2, pressurizing melting under the condition of 10～90 minutes hold-times, carry out the decomposition of crosslinking reaction and whipping agent after, make composition foaming by open mold, manufacture crosslinked foam one time.
Above-mentioned crosslinked foaming mould has no particular limits its shape, can use to have the mould that can obtain common sheet form.This crosslinked foaming mould must be complete airtight structure, so that do not emit the gas that produces when thermoplastic resin and whipping agent decompose.In addition, as template, consider that from the release property of resin preferred inner face has the template of taper.
A crosslinked foam that will obtain by aforesaid method is given its predetermined shape by compression molding.This moment the compression molding condition be, die temperature is 130～200 ℃, mold pressure is 30～300kgf/cm 2, compression time is 5～60 minutes, compression ratio is in 1.1～3.0 scopes.
The footwear parts
The footwear parts that the present invention relates to as mentioned above, are formed by the olefin type elastomer crosslinked foam that the present invention relates to.
As aforementioned footwear parts, for example can enumerate sole, the middle level sole of footwear, the internal layer sole of footwear, sole, sandals etc.
The effect of invention
According to the present invention, can provide ア ス カ one C hardness in 20～80 scopes, and low-gravity, (CS) is little in compression set, and the olefin type elastomer crosslinked foaming body and function elastic composition of the outstanding olefin type elastomer crosslinked foam of tear strength characteristic and resilience elasticity, and crosslinked foam.
In addition,, can provide the footwear parts that form by above-mentioned olefin type elastomer crosslinked foam, sole for example, the middle level sole of footwear, the internal layer sole of footwear, sandals etc. according to the present invention.
Embodiment
Below, the present invention will be described by embodiment, but the present invention is not limited to these embodiment.
For the crosslinked foam that obtains at embodiment and comparative example, measure proportion, compression set, tear strength, ア ス カ one C hardness (surface hardness) and resilience elasticity according to following method.In addition, measure gel ratio (gel content) according to preceding method.
(1) proportion of foam
According to JIS K 7222, measure proportion.
(2) compression set
According to JIS K 630, at 50 ℃ * 60Hr, carry out the compression set test under the condition of draught 50%, obtain compression set (CS).
(3) tear strength
According to BS 5131-2.6, carry out tear strength test draw speed 100mm/ minute condition, obtain tear strength.
(4) ア ス カ one C hardness
ア ス カ one C hardness is obtained according to " the spring hardness test C type test method " of attached book 2 records of JIS K7312-1996.
(5) resilience elasticity
Measure resilience elasticity according to JIS K6255.
In addition, as follows at the ethylene of embodiment and comparative example use.
(1) ethene butene-1 copolymer (Al)
MFR (1238,190 ℃ of ASTM D, loading 2.16kg)=0.5g/10 minute
Density (ASTM D 1505)=885kg/m 3,
Mw/Mn＝2.0
MFR 10/MFR 216＝6.0
(2) ethene butene-1 copolymer (A2)
MFR (1238,190 ℃ of ASTM D, loading 2.16kg)=0.5g/10 minute
Density (ASTM D 1505)=885kg/m 3,
Mw/Mn＝2.1
MFR 10/MFR 2.16＝10.4
(3) ethene butene-1 copolymer (A3)
MFR (1238,190 ℃ of ASTM D, loading 2.16kg)=3.6g/10 minute
Density (ASTM D 1505)=895kg/m 3,
Mw/Mn＝2.1
MFR 10/MFR 216＝5.7
(4) ethene butene-1 copolymer (A4)
MFR (1238,190 ℃ of ASTM D, loading 2.16kg)=3.6g/10 minute
Density (ASTM D 1505)=895kg/m 3,
Mw/Mn＝2.0
MFR 10/MFR 216＝8.3
(5) ethene butene-1 copolymer (A5)
MFR (1238,190 ℃ of ASTM D, loading 2.16kg)=1.2g/10 minute
Density (ASTM D 1505)=905kg/m 3,
Mw/Mn＝2.1
MFR 10/MFR 2.16＝5.9
(6) ethene 1-hexene copolymer (A6)
MFR (1238,190 ℃ of ASTM D, loading 2.16kg)=1.3g/10 minute
Density (ASTM D 1505)=905kg/m 3,
Mw/Mn＝3.0
MFR 10/MFR 2.16＝6.5
[embodiment 1]
With above-mentioned ethene butene-1 copolymer (Al) 25 weight parts, above-mentioned ethene butene-1 copolymer (A3) 45 weight parts, above-mentioned ethene 1-hexene copolymer (A6) 30 weight parts, zinc oxide 3 weight parts, stearic acid 1 weight part, titanium dioxide 4 weight parts, two cumenyl superoxide, 0.6 weight part, triallyl cyanurate 0.15 weight part, azoformamide 7.0 weight parts, be set at 2 rollers of 120 ℃ after mixing 10 minutes with zinc acrylate resin 0.4 weight part with the roller surfaces temperature, be configured as lamellar.
The gained thin plate is filled in the pressurizing mold, at 150kg/m 2, 155 ℃, 30 minutes condition, pressurized, heated obtains crosslinked foam one time.This pressurizing mold is of a size of thickness 15mm, long 150mm, wide 200mm.
Then, with this crosslinked foam at 155 ℃, 150kg/cm 2The condition lower compression be shaped 10 minutes, obtain the secondary crosslinking foam.Gained secondary crosslinking foam is of a size of thickness 15mm, long 160mm, wide 250mm.
Then, measure the proportion of this secondary crosslinking foam according to the method described above, compression set, tear strength, ア ス カ one C hardness, resilience elasticity and gel ratio.Its result is as shown in table 1.
[embodiment 2]
Except in embodiment 1, use above-mentioned ethene butene-1 copolymer (A2) 25 weight parts to replace ethene butene-1 copolymer (A1) 25 weight parts, in addition, use above-mentioned ethene butene-1 copolymer (A4) 45 weight parts to replace carrying out similarly to Example 1 beyond ethene butene-1 copolymer (A3) 45 weight parts.The result is as shown in table 1.
[embodiment 3]
With above-mentioned ethene butene-1 copolymer (Al) 18.8 weight parts, above-mentioned ethene butene-1 copolymer (A3) 50 weight parts, above-mentioned ethene 1-hexene copolymer (A6) 31.2 weight parts, above-mentioned high-pressure process new LDPE (film grade) [HPLDPE: density (ASTM D 1505)=920kg/m 3MFR (1238,190 ℃ of ASTM D, 2.16kg loading)=3.0g/10 minute] 25 weight parts, zinc oxide 3 weight parts, stearic acid 1 weight part, titanium dioxide 4 weight parts, two cumenyl superoxide, 0.6 weight part, triallyl cyanurate 0.15 weight part, azoformamide 7.0 weight parts and zinc acrylate resin 0.4 weight part are set at 2 rollers of 120 ℃ after mixing 10 minutes with the roller surfaces temperature, are configured as lamellar.
The gained thin plate is filled in the pressurizing mold, at 150kg/cm 2, 155 ℃, 30 minutes condition, pressurized, heated obtains crosslinked foam one time.This pressurizing mold is of a size of thickness 15mm, long 150mm, wide 200mm.
Then, with this crosslinked foam at 155 ℃, 150kg/cm 2Condition compression molding 10 minutes, obtain the secondary crosslinking foam.Gained secondary crosslinking foam is of a size of thickness 15mm, long 160mm, wide 250mm.
Then, measure the proportion of this secondary crosslinking foam according to the method described above, compression set, tear strength, ア ス カ one C hardness, resilience elasticity and gel ratio.Its result is as shown in table 1.
[comparative example 1]
Except in embodiment 1, do not use beyond the zinc acrylate resin, carry out similarly to Example 1.The result is as shown in table 1.
Table 1
Embodiment 1 Embodiment 2 Embodiment 3 Comparative example 1
The composition of elastic composition [weight part] multipolymer (A1) 25 - 18.8 25
Multipolymer (A2) - 25 - -
Multipolymer (A3) 45 - 50 45
Multipolymer (A4) - 45 - -
Multipolymer (A6) 30 30 31.2 30
HPLDPE - - 25 -
Zinc oxide 3 3 3 3
Stearic acid 1 1 1 1
Titanium dioxide 4 4 4 4
Two cumenyl superoxide 0.6 0.6 0.6 0.6
The triallyl cyanurate 0.15 0.15 0.15 0.15
Azoformamide 7.0 7.0 7.0 7.0
Zinc acrylate resin 0.4 0.4 0.4 -
Physical properties proportion [the g/cm of secondary crosslinking foam 3] 0.13 0.13 0.14 0.13
Gel ratio [%] 86 84 84 78
ア ス カ one C hardness 55 57 61 55
Tear strength [kg/cm] 3.1 3.0 3.3 2.7
Compression set [%] 38 40 37 43
Resilience elasticity [%] 65 65 62 62
[embodiment 4]
With above-mentioned ethene butene-1 copolymer (A3) 33.3 weight parts, above-mentioned ethene 1-hexene copolymer (A6) 66.7 weight parts, ethene vinyl-acetic ester multipolymer [EVA; Vinyl-acetic ester content=21 weight %, MFR (1238,190 ℃ of ASTM D, 2.16kg loading)=1.5g/10 minute] 122 weight parts, zinc oxide 3 weight parts, stearic acid 1 weight part, titanium dioxide 4 weight parts, two cumenyl superoxide, 0.6 weight part, triallyl cyanurate 0.15 weight part, azoformamide 6.5 weight parts and zinc acrylate resin 0.4 weight part are set at 2 rollers of 120 ℃ after mixing 10 minutes with the roller surfaces temperature, are configured as lamellar.
The gained thin plate is filled in the pressurizing mold, at 150kg/cm 2, 155 ℃, 30 minutes condition, pressurized, heated obtains crosslinked foam one time.This pressurizing mold is of a size of thickness 15mm, long 150mm, wide 200mm.
Then, with this crosslinked foam at 155 ℃, 150kg/cm 2Condition compression molding 10 minutes, obtain the secondary crosslinking foam.Gained secondary crosslinking foam is of a size of thickness 15mm, long 160mm, wide 250mm.
Then, measure the proportion of this secondary crosslinking foam according to the method described above, compression set, tear strength, ア ス カ one C hardness, resilience elasticity and gel ratio.Its result is as shown in table 2.
[embodiment 5]
Except in embodiment 4, use ethene butene-1 copolymer (A5) 66.7 weight parts to replace carrying out similarly to Example 4 beyond ethene 1-hexene copolymer (A6) 66.7 weight parts.The result is as shown in table 2.
[comparative example 2]
Except in embodiment 4, do not use beyond the zinc acrylate resin, carry out similarly to Example 4, the result is as shown in table 2.
[comparative example 3]
Except in embodiment 5, do not use beyond the zinc acrylate resin, carry out similarly to Example 5, the result is as shown in table 2.
Table 2
Embodiment 4 Embodiment 5 Comparative example 2 Comparative example 3
The composition of elastic composition [weight part] multipolymer (A3) 33.3 33.3 33.3 33.3
Multipolymer (A5) - 66.7 - 66.7
Multipolymer (A6) 66.7 - 66.7 -
EVA 122 122 122 122
Zinc oxide 3 3 3 3
Stearic acid 1 1 1 1
Titanium dioxide 4 4 4 4
Two cumenyl superoxide 0.6 0.6 0.6 0.6
The triallyl cyanurate 0.15 0.15 0.15 0.15
Azoformamide 6.5 6.5 6.5 6.5
Zinc acrylate resin 0.4 0.4 - -
Physical properties proportion [the g/cm of secondary crosslinking foam 3] 0.14 0.14 0.14 0.14
Gel ratio [%] 85 86 79 80
ア ス カ one C hardness 54 55 55 55
Tear strength [kg/cm] 3.0 3.0 2.6 2.6
Compression set [%] 43 43 47 47
Resilience elasticity [%] 62 61 56 57

Claims (17)

1. olefin type elastomer crosslinked foaming body and function elastic composition, it comprises:
Ethylene (A), described ethylene (A) contains the unit that derives from ethene of 85-99 mole %, and its density that records by ASTM D 1505 methods is 880～920kg/m 3, the melt flow MFR that under 190 ℃, the condition of 2.16kg loading, records by ASTM D 1238 methods 2.16Be 0.1～10g/10 minute,
Optional high-pressure process new LDPE (film grade) (B), described high-pressure process new LDPE (film grade) (B) contains the unit less than the alpha-olefin that derives from carbonatoms 3～10 of 1 mole of %, and it is 0.1～50g/10 minute by the melt flow that ASTM D1238 method records under 190 ℃, the condition of 2.16kg loading
Optional ethene vinyl-acetic ester multipolymer (C), the melt flow that the vinyl-acetic ester content of described ethene vinyl-acetic ester multipolymer (C) is 10～30 weight %, record under 190 ℃, the condition of 2.16kg loading by ASTM D 1238 methods is 0.1～50g/10 minute
Organo-peroxide (D),
Crosslinking coagent (E),
Whipping agent (F) and
Organometallic compound (G),
Described organometallic compound (G) is the metallic compound that is selected from the periodic table of elements 2～12 families, in a part, have at least 2 groups that contain unsaturated carbon bond and be selected from O, S and at least a atom of N, with respect to above-mentioned ethylene (A), high-pressure process new LDPE (film grade) (B) and ethene vinyl-acetic ester multipolymer (C) sum 100 weight parts, described organometallic compound (G) is the 0.05-5 weight part.
2. according to the elastic composition of claim 1 record, it is characterized in that with respect to described ethylene (A) 100 weight parts, described high-pressure process new LDPE (film grade) (B) is 5～100 weight parts.
3. elastic composition according to claim 1 and 2 is characterized in that, with respect to described ethylene (A) 100 weight parts, described ethene vinyl-acetic ester multipolymer (C) is 5～1900 weight parts.
4. according to the elastic composition of claim 1 or 2 records, it is characterized in that the alpha-olefin in the described ethylene (A) is the alpha-olefin of carbonatoms 3～10.
5. according to claim 1 or 2 elastic compositions of putting down in writing, it is characterized in that described ethylene (A) is the melt flow MFR that the molecular weight distribution mw/mn obtained by gel permeation chromatography more than 2 kinds records under 190 ℃, the condition of 2.16kg loading in 1.5～4 scope and by ASTM D 1238 methods 2.16With the melt flow MFR that under 190 ℃, the condition of 10kg loading, records by ASTM D 1238 methods 10Ratio MFR 10/ MFR 2.16The mixture of the ethylene in 5～20 scope.
6. according to the elastic composition of claim 3 record, it is characterized in that described ethylene (A) is the melt flow MFR that the molecular weight distribution mw/mn obtained by gel permeation chromatography more than 2 kinds records at 190 ℃, 2.16kg loading in 1.5～4 scope and by ASTM D 1238 methods 2.16With the melt flow MFR that under 190 ℃, the condition of 10kg loading, records by ASTM D 1238 methods 10Ratio MFR 10/ MFR 2.16The mixture of the ethylene in 5～20 scope.
7. according to the elastic composition of claim 5 record, it is characterized in that the described molecular weight distribution mw/mn that the mixture of ethylene is obtained by gel permeation chromatography more than 2 kinds is in 2.3～6 scope, by mixing or the multi-stage polymeric manufacturing.
8. according to the elastic composition of claim 6 record, it is characterized in that the described molecular weight distribution mw/mn that the mixture of ethylene is obtained by GPC more than 2 kinds is in 2.3～6 scope, by mixing or the multi-stage polymeric manufacturing.
9. according to the elastic composition of claim 1 record, it is characterized in that described organometallic compound (G) has at least 2 CH in a part 2=CH-CO-O-base or CH 2=C (CH 3)-CO-O-base.
10. according to the elastic composition of claim 9 record, it is characterized in that described organometallic compound (G) is an organic zinc compound.
11. the elastic composition according to claim 10 record is characterized in that described organic zinc compound is dizinc acrylate resin or zinc dimethacrylate.
12. the olefin type elastomer crosslinked foam is characterized in that, it obtains the olefin type elastomer crosslinked foaming body and function elastic composition crosslinked foaming of each record in the claim 1～11.
13. the olefin type elastomer crosslinked foam is characterized in that, it obtains the crosslinked foam second-compressed of claim 12 record.
14. the olefin type elastomer crosslinked foam according to claim 13 record is characterized in that described second-compressed is at 130 ℃～200 ℃ of temperature, 30～300kgf/cm 2Carry out under loading, 5～60 minutes the condition.
15. olefin type elastomer crosslinked foam according to each record in the claim 12～14, it is characterized in that its proportion that records by JIS K 7222 methods is 0.05～0.25, surface hardness is represented with A Si card C hardness, be 20～80, the gel ratio is more than 70%.
16. the footwear parts is characterized in that, are formed by the crosslinked foam of each record in the claim 12～15.
17. the footwear parts according to claim 16 record is characterized in that described footwear parts are middle level sole, internal layer sole or sole.
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